Department of Chemistry, Stanford University, 333 Campus Drive, Stanford, CA, 94305, USA.
Angew Chem Int Ed Engl. 2016 Sep 12;55(38):11476-9. doi: 10.1002/anie.201605722. Epub 2016 Aug 10.
The brominated chamigrene sesquiterpenes constitute a large subclass of bromocyclohexane-containing natural products, yet no general enantioselective strategy for the synthesis of these small molecules exists. Herein we report a general strategy for accessing this family of secondary metabolites, including the enantioselective synthesis of (-)-α- and (-)-ent-β-bromochamigrene, (-)-dactylone, and (+)-aplydactone. Access to these molecules is enabled by a stereospecific bromopolyene cyclization initiated by the solvolysis of an enantiomerically enriched vicinal bromochloride.
溴代环庚烯倍半萜构成了含溴环己烷天然产物的一个大类,但目前还没有针对这些小分子的通用对映选择性合成策略。在此,我们报告了一种获得这类次级代谢产物的通用策略,包括对映选择性合成 (-)-α-和 (-)-ent-β-溴环庚烯、(-)-达可酮和 (+)-阿朴多酮。通过对映体富集的邻溴氯代物的溶剂解引发的立体特异性溴聚烯烃环化反应,实现了这些分子的获得。